JPH03196135A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen the fluctuation in the sensitivity and fogging during the period of the preservation of the photosensitive material with lapse of time by producing a silver halide emulsion, which is prepd. to 5.0 to 11.0pH, by stages exclusive of chemical sensitization and a stage in which at least one kind of oxidizing agents to silver exist. CONSTITUTION:The pH of the silver halide emulsion is 5.0 to 11.0. The silver halide emulsion is produced by the stages exclusive of the chemical sensitization and the stage in which at least one kind of the oxidizing agents to silver exist. The addition of the oxidizing agents to the silver during the production process is executed by preparing, for example, water soluble compds. as an aq. soln. of an adequate concn., dissolving the compds. into a suitable org. solvent, for example, a solvent, such as alcohol, which does not adversely affect photographic characteristics and adding the compds. in the form of the solution to the silver. The pH of the silver halide emulsion in the stage for forming the particles thereof is 5.0 to 11.0 and the formation of the particles of the silver halide emulsion is possible by adequately controlling pBr according to various purposes. The pBr in the particle formation stage of the silver halide emulsion is set at 2.0 to 5.0 and the timing when the oxidizing agents are added to the silver is preferable in the stage when the pBr attains 2.0 to 5.0. The high sensitivity and the less fogging are obtd. in this way. In addition, the fluctuation in the sensitivity and the fogging is lessened.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material that has high sensitivity and little fog (and has low sensitivity and fog during storage of the light-sensitive material). This invention relates to a silver halide photographic material with little variation in .

[Prior art]

Regarding the v4 manufacturing method of silver halide emulsions, many methods have been known to those skilled in the art, and there are many descriptions in known literature. For example, P.
des (written by Graf Kidek [Photograph X (7) Chemistry and Things Ft
J (Chimie et Physique Pho
tographl-que) (Paal Monte1
Inc., 1967), G.F.

"Chemistry of Photographic Emulsions J Ph.
oto-graphic Emul@ion Chem
istry) (FocalPress, 1966)
, V. L. Zellkman
“Preparation and Coating of Photographic Emulsions” by et al.
and Coating Photographic
Emt+-15jan) (Foal Press, 1964), etc., have many descriptions regarding the preparation method. Specifically, known types of silver halides include silver bromide, iodide complex, silver chloride, and mixed crystals of two or more of these, such as silver iodobromide and silver chlorobromide. g
As an atmosphere made of Mi, 1 [I do not know whether it is an injection method, a neutral method, an ammonia method, etc., and a method for reacting a soluble silver salt and a soluble halide salt is a single jet method, a double jet method, or a combination thereof. Are known. Also known is the so-called Chondrold double jet method in which the concentration of fixed ions is kept constant during the production of silver halide crystals.

In general, the acid method produces silver halide crystal grains with relatively fine grains and low sensitivity. (And conversely, the ammonia method is often used for MIm of relatively large and highly sensitive silver halide crystal grains. Ammonia forms complex ions with silver ions. The solubility of silver halide is high, and large grains can be easily grown.

In particular, the ammonia method is often used for highly sensitive silver iodobromide, which has low solubility.

However, if ammonia is used in VT4, the pH of the system will inevitably increase, causing the problem of easy fogging.

-1. The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, (111) it is necessary to increase the number of photons absorbed by each grain, (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (latent gI), and ( 3) In order to effectively utilize the formed latent image, development activity may be increased, but in order to increase sensitivity without deteriorating graininess, it is necessary to increase the efficiency of converting photoelectrons into latent images, that is, quantum It is most preferable to increase sensitivity. In order to increase Doji sensitivity, it is necessary to eliminate inefficiencies such as recombination and latent image dispersion as much as possible. Small silver nuclei with no development activity are placed inside or on the surface of silver halide. It is known that the method of reduction sensitization is effective in preventing recombination, and has been studied since ancient times. For example, Co1N@r (Korea) is
ic 5elence and Engineerin
g23, page 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods.

She used dimethylamine borane, stannous chloride, hydrazine, high aging, and low pAg aging.

Here, it is described that by reducing sensitizing octahedral silver bromide under high P)'1 conditions and introducing scissor nuclei, sensitivity increases due to electron capture.

Also, Journ by H, W, Wood
al ofPhotographle 5science
(Journal of Photographic Science) 1.163 (1953) has low or high PAg.
It has been reported that the sensitivity of silver bromide emulsions and silver chlorobromide emulsions is increased by The method of reduction sensitization is further described in U.S. Pat. No. 2,518,698, U.S. Pat.
No. 777, 1is1 No. 3.930,867.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of the shelf life of light-sensitive materials. Regarding the technology for improving the storage stability of reduction-sensitized emulsions, Japanese Patent Application Laid-Open No. 57-828
No. 31 and No. 60-178445, but it has not reached a sufficient level of improvement.

After the grain formation process, silver halide emulsions require a desalination washing process to remove soluble salts.

Nowadays, flocculation rinsing is commonly used to replace the time-consuming classical terdel rinsing method. In the case of washing with water by flocculation, in order to increase the sedimentation rate, K and a sedimentation agent such as a surfactant are usually added to lower the -. This method utilizes the fact that gelatin adsorbs less on silver halide and reduces the protective colloid effect. However, if - during sedimentation is lowered, R, J, Croome (
Journal of Photo
graphic 5science (journal op.
Photographic Science) 31.30 (198
3) causes a decrease in photographic sensitivity. Also, Zbuang Si-yong and L%u X
ing-gin is also Proc@*d-kngs of t
he International Congrvsi
ofPhotographic 5science,
Koln (Cologne) jp124 (1986)
pointed out a decrease in photographic sensitivity when sedimentation was carried out with a lower value of -, and reported that photographic sensitivity increased when sedimentation was performed in a lower μL amount in the coexistence of ammonium sulfate. but,
In this case as well, it is highly likely that the storage stability of the photosensitive material using this emulsion will be a problem.

As mentioned above, when silver halide emulsions are exposed to a high-(or low-p, Ag) reducing atmosphere for various purposes (particularly to increase sensitivity), high sensitivity can be achieved.
The storage stability of light-sensitive materials using these emulsions has sometimes been problematic.

[Problem H that the present invention attempts to solve]

Conventional methods for preparing emulsions aimed at increasing sensitivity and improving image quality have had the problem of large fluctuations in sensitivity and fog when photographic materials containing such emulsions are stored over time.

An object of the present invention is to provide a photographic material with high sensitivity and less fog. Another object of the present invention is to provide a photographic light-sensitive material with excellent stability over time with little fluctuation in exposure and fog, from the time of production to the time of use (exposure) and to the time of post-exposure processing. The goal is to provide the following.

[Lesson l! /! [Means to solve]

The present inventors have discovered that the object of the present invention can be achieved by the following method.

(At least one silver halide emulsion N on the support 11)
In a silver halide photographic light-sensitive material having a pH of 5.
0 to 11.0, and is produced through a process other than chemical sensitization and a process in which at least one oxidizing agent for silver is present.

(2) An oxidizing agent for silver, or the general formula c i ), (
:II:1 or at least one of the compounds represented by [:m)
The silver halide photographic material described in calculation term (1), which is fjl.

(1) R-8028-M CII) R-8028-R' CIU) R-SOS-Lm-8802-12 In the formula, R
, R, and R#'i may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group; M represents an aliphatic group, an aromatic group, or a heterocyclic group; L represents an aromatic group or a heterocyclic group, and m is O or 1.

Compounds of general formulas [1] to [1,1] are divalent groups derived from the structures represented by [1) to [m]? It may also be a polymer containing it as a repeating unit.

(3) In the manufacturing process of silver halide emulsion, the pH is 5.
12. The silver halide photographic material according to claim 11, wherein the step in which the particle size is 60 to 11.0 is a grain forming step.

(4) Comments on the grain formation process of silver halide emulsions from 62 to
11.0. The silver halide photographic material according to claim 3, wherein the silver halide photographic material has a molecular weight of 11.0.

(5) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in the silver halide emulsion layer has a pBr of 2.0 to 5 at the time of grain formation. A silver halide photographic light-sensitive material characterized in that it is manufactured through a step in which the oxidizing agent is .0, and at least one oxidizing agent is present.

(6) Oxidizing agent power on silver, general formula (1), Ell
) or [III3] The silver halide photographic material according to claim (5).

(1]]R-SO2S-M II) R-802S-R' [m) R-8028-Lrn-8SO2-R2 In the formula, R, R, and R may be the same or different (, aliphatic group,
Represents an aromatic group or a heterocyclic group, and represents an MFi cation. L represents an aromatic group or a heterocyclic group, m is O or F
It is il.

Compounds of general formulas [1] to [m] are [1] to [
It may also be a polymer containing as a repeating unit a divalent group derived from the structure shown in [m].

(7) In the manufacturing process of silver halide emulsions, pH
is 5.0 to 11.0 is a desalination water washing step.
The silver halide zero-truth ft, feather material according to claim (1).

(8) In the manufacturing process of silver halide emulsion, the pH is
The silver halide photographic material according to claim 7, which has a molecular weight of 6.2 to 11.0.

(9) In the manufacturing process of silver halide emulsions, pH
2. The silver halide photographic material according to claim 1, wherein the step in which is from 5.0 to 11.0 is a redispersion step.

The pH of the αG silver halide emulsion redispersion step is 62.
The silver halide photographic material according to claim 9, wherein the silver halide photographic material has a molecular weight of 11.0 to 11.0.

The present invention will be explained in detail below.

The oxidizing agent for silver in Kenmei is a compound that acts on metallic silver to convert it into silver ions. Particularly effective are compounds that convert extremely minute iron atoms produced as a by-product during the process of forming silver halide grains into iron ions. The silver ions generated by this process may form silver salts that are poorly soluble in water, such as silver halide, silver sulfide, and silver selenide.
Further, a water-easily soluble silver salt such as nitrate silver may be formed.

The oxidizing agent for silver may be inorganic or organic. Examples of inorganic oxidizing agents include ozone, hydrogen peroxide, and adducts thereof (e.g., NaBO2.H2O2.3H
20,2Na COs・3H202, NIL4P207
-2H20□, 2Na2SO4eH20□・2H20)
, peroxygens (e.g., K2S2O8, K2C2O
4, K4P2O7), oxidized complex compounds (e.g.
K2(Ti(O□)C204]・3H20,280 on 4
4-Tl(0□)OH@5o4-2H20, Na3[v
O(02)(C204)2・6H20], over-r 7
canyate (e.g. KM n O4), chromate (e.g. KM n O4), chromate (
For example, oxyacids such as K2c r 207), halogen elements such as Kumioki and bromine, perhalates (for example,
(potassium periodate), high valence metals (e.g. potassium hexacyanoferric acid) and thiosulfonates.

In addition, examples of organic oxidizing agents include quinones such as p-quino 7, organic peroxidants such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-10 musaximide, chloramine T1, chloramine B). Examples include:

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic shading agents such as theosulfonate, and organic oxidizing agents such as quinones.

A more preferred oxidizing agent is thiosulfonic acid salt, which can be selected from compounds represented by formulas [summer] to [m]. Among these, the most preferred is the compound represented by formula [1].

(rlR-so□S-MCU]]R-SO2S-R'C[[l]R-SO2S-Lm-8802-R2In the formula, R, R, and R may be different in the same way, and fat represents a group group, an aromatic group, or a heterocyclic group, and represents an MFi cation.L represents a divalent linking group V, and m represents OX, which is 1.

The compound of general formula (1) to III) is a divalent group derived from the structure represented by (H to 1) or II
It may also be a polymer containing a divalent group derived from the structure shown in I) as a repeating unit. Further, when possible, R, R, R, and L may be bonded to each other to form a ring.

To further explain the thiosulfonic acid compounds of general formulas (1), (II) and (11), R2R1 and R
is a combination of an aliphatic group, a saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, or an alkyl group having 2 to 22 carbon atoms. are alkenyl groups and alkynyl groups, which may have a substituent. Examples of alkyl groups include methyl,
Ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isonoropyl, and t-butyl are available.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include glopargyl and butynyl.

R* The aromatic group for R' and R2 includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms.
Examples include phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R and R is 3 to 15 having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium and having at least one carbon atom.
It is a membered ring, preferably a 3- to 6-membered ring,
Examples include pyrrolidine, biiridine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole,
Examples include benzimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiazazole rings.

Substituents for R, R and R include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, octyloxy), aryl groups [e.g. phenyl, naphthyl, tolyl]. , hydroxy groups, halodane atoms (e.g. fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy), alkylthio groups (e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. , acetyl, globionyl, butyryl, valeryl],
Sulfonyl MC examples include methylsulfonyl, phenylsulfonyl), acylami/7i5 (e.g. acetylamino, benzoylamino), sulfonylamino groups (e.g. methanesulfonylamino, benzenesulfonylamino), acyloxy groups (e.g. acetoxy, benzoxy), carmexyl group, cyano group, sulfo group, amino group,
-3028M group, (indicates a Ma monovalent cation) -SO
2R' group is mentioned.

The aromatic group or heterocyclic group represented by L is C
,N.

An atom or atomic group containing at least one selected from S and 0. Specifically, alkylene group, alkenylene group, alkynylene group, arylene group, -O--8--N
It consists of H--CO--802-, etc., alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include -G-CH2,5- (n=1 to 12), -CH2-CH=CH-C
Examples include H2-CI (2CmiCCH2). Examples of the divalent aromatic group for L include a phenylene group and a naphthylene group.

These de-substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (ammonium, tetramethylammonium, tetrabutylammonium, etc.), phosphonium ions (tetraphenylphosphonium), and guanidyl groups.

When the general formula (1) to m) is a polymer, the following are examples of repeating units.

1+CH-CH2+ C02CH2CH20CH2CH2SO□SMH3 1+C-CH2+ CO2CH2CH2 -3o2R (C-CH2) 8028M These polymers are It may be a homopolymer, It may also be a copolymer with other copolymerizable monomers.

Specific examples of compounds represented by general formula (1), (II) or (m) are listed in Table A, but the invention is not limited thereto.

Compounds of general formulas [I], [II] and (DI) are %
1972-1019: British Patent 972,211: Jou
rnal of Organic Chemistry
y (Journal Op Organic Chemistry)
It can be easily synthesized by the method described in Vol. 53, p. 396 (1988).

The amount of the oxidizing agent added to silver in the present invention is silver halide 1
It is preferable to add 10 to 10 moles.

More preferred is 10 to 10-2 mol, particularly preferred is 10 to 10-3 mol.

In order to add the oxidizing agents represented by general formulas (1) to (1G) during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or dissolvable in water are dissolved in suitable organic solvents that are miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and do not adversely affect photographic properties. However, it can be added as a solution.

Table A (1-1) CH3So2SNm (1-2) C2H5So□SNm (1-3) C3H,5o2SK (1-4) C4H,80□5Li (1-5) C6H,3802SNa (1-6) C' 8H,, SO□5Na (1-7) 2H5 (1-s)c, 0H21so2sNa(1-9)C1
2R25802SN& (1-10)C16H,3SO2SNa (I-11) (1-12) t-C4H,5O2SNa (1-13) CH0CH2CH2SO2S@Na (1-15) C) (=CHC)12SO□Na (1-16 ) (1-17) (1-18) (I-19) (1-20) (1-21) (1-22) (1-23) (l-24) (1-25) (1-26 ) (I-27) (1-28) (1-29) KSS02(CH2)2S028K (f-30) NaSSO2(Cl2) 4So2SNm(I-31) NaSSO2(CH2)48(CH2)4so2sNa
(1-32) S O2S N m (I-33) (It-1) CH80S-CM3 2 5 2 (II-2) C8H17SO□5CH2CI(.

(II-3) CD-4) (n-5) C2H5SO2SCH2CH2CN (Ii-6) (If-7) CM.

CHSo 5C) ICH2ON 4 9 2 (II-8) (II-9) (lt-10) (II-11) (n-12) (II-13) (It-14) (II-15) (It- 16) (n-17) (If-18) C2H5S02SCH2CH2CH2CH20H(It
-19) (II-20) (II-21 CH35SO□(CH2)4So28CH3Cm-22
) CH38802(CH2) 2So28CH.

(It-23) (■ 24) x: 7=z, /1 (molar ratio) (U-25) SO2・S (m-1) (III-2) C2H5SO2SCH2CH2SO2CH2CH2SS
O2C2H5 (III-3) (III-4) CH2CH20H (III-5) (II-6) (m-7) C2R5S02SSS02C2H5 (fil-8) (n) C, H, 5o2SSSO7C, H, (+) (II
I-9) The manufacturing process of silver halide emulsions includes grain formation, desalination washing,
It is broadly divided into processes such as redispersion, chemical sensitization, and coating.

The silver halide emulsion L used in the present invention is obtained by going through a step of -5.0 to 11.0 at any stage of the manufacturing process other than chemical sensitization, and adding an oxidizing agent for silver. Here, - is defined as the common logarithm of the reciprocal of the hydrogen ion concentration, and for its measurement, generally a single pond is made by combining a glass electrode and a straight pole, and its movement 1. There is no way to measure the force and find it easily using a commercially available internal measuring device! can be determined.

The oxidizing agent may be added to the scissors at the final stage of the silver halide emulsion manufacturing process. Preferably, it is added in the step of -5,0 to 11.0, and more preferably, it is added before the step of #1Pk4s, o to 11.0, or at the first stage, and -5,0 ~
11.0 is to coexist in the process. here,
If there is a step exceeding -11.0, even if an oxidizing agent for the chains is added, fog will increase and large temporal changes will occur, making it impossible to obtain the effects of the present invention, which is not preferable.

Also, p! (In the case of a school where the process with s, o~11.0 is a chemical sensitization process, the effect of this IQK is small, so in the present invention, it is limited to processes other than chemical sensitization.

In the manufacturing process of silver halide emulsion, phs.

It is preferable that the step in which the particle size is ˜11.0 is a particle forming step. This agreement is between -50 and 11.0, regardless of whether it is in all stages of the particle formation process or in some stages.
The oxidizing agent is preferably added to silver at any stage of the grain formation process, and more preferably from pt 15.0 to 11.
．． It is to be added at the stage when it becomes 0, and it is preferably added just before the stage when it becomes -50 to 11°0, or at the beginning of Fi, and it coexists at the stage when it becomes -5,0 to 11.0. It is to let

It is also possible to add it to the reaction vessel in advance (but it is preferable to add it at an appropriate time of particle formation.Also, add the oxidizing agent for the button in advance to the aqueous solution of the water-soluble complex salt or water-soluble alkali halide, Particles may be formed using these aqueous solutions, and it is also preferable to add the solution of the bone thickening agent in several portions or continuously over a long period of time during particle formation. .

Preferred oxidizing agents for the present invention have general formulas [I] to [
111], and the most preferred compound is a compound represented by the general formula [I].

In the photographic emulsion layer of the photographic light-sensitive material used in the invention i, any of 710 silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide, silver bromide, and silver chlorobromide containing 30 molar or less iodide needles.

The silver oxide grains used in the present invention may be normal crystals that do not contain twin crystals 'rI7n, as explained in 9.163, edited by the Photographic Society of Japan, edited by Yoshin Shio, Basics of the Photographic Industry (Corona Publishing). For example, a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a nonparallel multiple twin with two or more nonparallel twin planes, etc. You can choose and use it according to your needs. In the case of normal crystals, there are cubic particles consisting of (100) planes, octahedral particles consisting of (111) planes, and dodecahedral particles consisting of (110) planes disclosed in Japanese Patent Publication No. 55-42737 and Japanese Patent Publication No. 60-222842. Can be used. Furthermore, Journal of Imagi
ng3eience volume 30 247-'-ji 1986
(211) as reported in 2007 is representative (b
ll) plane particles, (hhl) plane particles with (331) planes as a representative, (hko) plane particles with (210) planes as representative, and (hkl) plane particles with (321) planes as representatives were also prepared by devising the preparation method. However, it can be selected and used depending on the purpose. (100) and (Ill) planes coexisting in one particle, tetradecahedral particles, (100) and (110) planes coexisting, (111) planes and (110) planes coexisting, etc. Particles in which one surface or many surfaces coexist can also be selected and used depending on the purpose.

The grain size of silver halide may be fine grains of o,x microns or less, or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

A so-called monodisperse silver emulsion having a narrow grain size distribution, in which 500 ts or more of all grains are within ±30 inches of the average grain size in terms of grain number or weight, can be used in the present invention. In addition, in order to satisfy the goal of light-sensitive materials, two or more types of monodispersed silver emulsions with different grain sizes are used in the -(- layer) in emulsion layers having practically the same color sensitivity. Mix or layer in separate layers
I can clothe it. Furthermore, polydispersity of 2 or more layers)・
Silver rognide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or used in one layer.
The photographic emulsion used in the book is ``Physics and Chemistry of Photography'' by Gura7 Kide, published by Beaumontel (P.

G1afkid@s+Chimis at Physi
que photogra-phiqu@Paul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.

F, Duffin+ Photograph E
Mulsion Chsmi-stry (Focal
Press+ 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Vol. 1 Cal Press (V,
L, Z@likman et al., Making
andCoating Photographic g
mulsion+ FocalFresco 1964
) etc. In other words, any of the acid method, medium injection method, ammonia method, etc. can be used. Any one-sided mixing method, side mixing method, combination thereof, etc. may be used. A method in which particles are formed under silver ion filtration (so-called back mixing method) may also be used. pAg in the liquid phase in which silver halide is produced as a mixing method
It is also possible to use a method of keeping 'lr' constant, ie the so-called control double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and - during grain formation. An example of this is Photographic Science and Engineering.
SeSene and Engineering@ering) Volume 6, pp. 159-165 (1962): Journal φ Op Photography Science (Journal
of Photographic 5science)
, vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. 1,413.
, No. 748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in the book by Creep [The Theory and Practice of Photography J (C1evs+Photo-grain).
pby Th@ory and Practices (
1930) ) + 131 pages; Gatoff, Photographic Science and Engineering (Cuto
ff.

Photographic 5science and
Engineering).

Volume 14, pp. 248-257 (1970): US Patent! No. 4,434,226, friH4,414,310
(B) No. 4,433.048, No. 4,439,52
Easily ¥Ml by the method described in No. 0 and National Patent No. 2,112.157! can do. Due to the use of tabular grains, there are advantages such as increased grain sensitivity and increased color sensitization efficiency using sensitizing dyes. It has been stated.

Tabular grains are preferred as emulsions of the present invention.

In particular, tabular grains in which grains with an aspect ratio of 3 to 8 occupy 50 inches or more of the total projected area are preferred.

The crystalline kojizuke grains may be similar to the grains or may have a layered structure in which the inside and outside have different halogen compositions.These emulsion grains are described in British Patent No.
No. 146, U.S. Patent No. 3.505°068, lir+
No. 4.444,877 and patent application No. 58-248469
Disclosed in the issue etc. Furthermore, silver halides with different compositions may be bonded by epitaxial bonding (
, or may be bonded with a compound other than silver halide, such as Rodan steel or lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or ridge structure in terms of halogen composition in its grains.

Typical examples are JP-B No. 43-13162 and JP-A No. 6.
1-215540, JP-A No. 60-222845, JP-A No. 61-75337, etc., these are core-shell type or two-rod type particles having different halogen compositions V in the inside and surface layers. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core has a cubic shape, and the shelled particles may have a cubic or octahedral shape. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. In addition, although the core part is a clearly regular particle, the shape of the shelled particle is slightly irregular (sometimes it is scratched or irregularly shaped. Also, it is not a mere double structure (disclosed in JP-A-60-222844). It is possible to make a multi-layer structure with 31 layers or more, or to apply a thin layer of silver halide having a different composition to the surface of the core-shell double layer particles.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526, EP199290A2
, Japanese Patent Publication No. 58-24772, Japanese Patent Application Laid-Open No. 59-16254, etc. The crystal to be bonded can have a composition different from that of the host crystal and can be bonded to an edge or a corner portion of the host crystal, or to the Fi surface.

Such a conjugate crystal can be formed even if the host crystal is uniform in halogen composition or has a core-shell structure.

In the case of a bonded structure, it is naturally possible to combine silver halide giants, but it is also possible to create a bonded structure by introducing a silver salt compound that does not have a rock #l structure, such as Rodan silver or carbonate button, with a halide ←. can. Further, a non-complex salt compound such as PbO may be used as long as a bonded structure is possible.

In the case of core-shell type silver iodobromide grains having these structures, the core part has a high silver iodide content and the shell part has a similar silver iodide content (but conversely, the core part has a high silver iodide content). The grains may have a low silver iodide content in the shell part and a high shell part.Similarly, grains with a bonded structure may have a high silver iodide content in the host crystal and a high silver iodide content in the bonded crystal. It may be a relatively low particle or vice versa.

In addition, the boundaries between particles with different halogen compositions having these structures may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
7B1% EP-0064412B1 or DE-2.
306447C2,! The surface may be modified as disclosed in Japanese Patent Publication No. 60-221320.

The silver halide emulsion used in the present invention is preferably a surface latent image type, but as disclosed in JP-A-59-133542, internal latent image
type emulsions can also be used. In addition, a shallow internal 1V type emulsion covered with a thin shell can also be used depending on the purpose.

silver rhodanide solvents are useful in promoting ripening.

For example, it is known to have an excess of rhodan ion present in the reactor to promote ripening. Therefore,
It is clear that ripening can be accelerated simply by introducing a halide #A solution into the reactor. Other ripening agents can also be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the addition of the silver and halide salts, and one or more ripening agents can be used. The halide salt and silver salt can also be introduced into the reactor along with the addition of a peptizer. Another variant is mature hushi,
The agent can also be introduced independently at the halide salt and silver salt addition steps.

Halodanized trowel solvents other than halogen ions include ammonia, thioethers, thioureas, AgI-soluble Th+ having a thiocarbonyl group, imidazoles,
Examples include sulfites and thiocyanates.

Specific compounds are shown below.

(1) H R (It) I (0-CH2-C12-8-CH2-CH2-8-C
I, -CH2-0H (III) 5CN (Fi/) (V) CH.

(Vl) 2S03 In order to obtain the preferable effects of the present invention, K is 5.0 to 11.0, more preferably 6.2 to 11.0. It is.

The silver halide emulsion of the present invention has pBr
Particles can be formed with appropriate control.

In order to obtain the preferable effects of the present invention, the pBr in the grain forming step of the silver halide emulsion is 2.0 to 5.0. In this case, the pBr may be 2.0 to 5.0 at all stages or at some stages of the particle formation process.

Further, the timing of adding the oxidizing agent to silver is preferably at any stage of the particle formation process, more preferably at the stage when par is 2.0 to 5.0, particularly preferably at the stage when pBr It is added just before or at the beginning of the stage where pBr becomes 2.0 to 5.0.
It is to make them coexist at the stage of ~5.0.

More preferable effects of the present invention can be obtained from pBr35 to
5.0. Moreover, further effects of the present invention can be obtained by combining the above-mentioned preferred or more preferred effects in one area.

To remove soluble salts from the emulsion after the grain formation step,
A desalination water washing step is required. As a normal desalting method, a Nudel water washing 7g curation sedimentation method, an ultrafiltration method, etc. can be used. It is also possible to use a salting-out method in which a large amount of a soluble salt such as ammonium sulfate is added and the - is significantly increased to cause precipitation.

In the production process of silver halide emulsions, the pH is 5.0 to 11.
．． It is also preferable for the present invention that the step in which the oxidizing agent becomes 0 is the demineralizing water washing step. In this case, it is preferable that the oxidizing agent is added to the radish at any stage of the desalting water washing step, more preferably. It is added immediately before or at the initial stage of the desalination washing process, and is allowed to coexist in all stages of the desalination washing process. Furthermore, when desalting is carried out by repeating sedimentation and water washing two or more times, it is preferable to add it immediately before each sedimentation and allow them to coexist.

In order to obtain the preferable effects of the present invention, pH 1 must be 5.0 to 11.0 in the silver halide emulsion manufacturing process.
0, more preferably 6.2 to 11.0.

The effect of the present invention is large in the above-mentioned salting-out method, which is extremely popular during demineralization and washing with water, and can improve the storage stability of photosensitive materials over time without reducing sensitivity.

The emulsion butterfly that has gone through the desalination water washing process is usually redispersed after adding gelatin and is chemically sensitized.

At the time of re-dividing, a method of increasing - is usually used in order to improve the flying of emulsion grains, but in this case as well, the storage stability of the light-sensitive material over time may be deteriorated. Therefore, in the manufacturing process of silver halide emulsions, -5.0 to 11.
It is also preferable for the present invention that the process in which the value becomes 0 is a dispersion process. In this case, the oxidizing agent is preferably added to the scissors at any stage of the dispersion process, and more preferably, it is added immediately before or at the beginning of the dispersion process so that it coexists in all stages of the dispersion process. be.

In order to obtain the preferable effects of the present invention, - in the dispersion step of the silver halide emulsion is from 5.0 to 11.0, more preferably from 6.2 to 11.0.

In the present invention, chemical sensitization, which is equivalent to sulfur sensitization and gold sensitization, is extremely superimposed, and a remarkable effect is obtained when chemical sensitization is performed. The location where chemical sensitization is applied varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion. When chemically sensitizing nuclei are embedded inside the particles, when tK5 is embedded shallowly from the particle surface, or when chemically sensitizing nuclei are formed on the surface.

Although it is effective to achieve the effects of the present invention, it is particularly preferable to create chemically sensitized nuclei near the surface. In other words, surface fP4 image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization is described in James (T, H, Jam@s), The Photographic Grosses, 4th edition, published by Macmillan, 1977, (T, H, Jam@5sTh
@Theory of th@Photography
c Pr@tests4 th *d, Maemllll
am, 1977) 6, p. 76, or as described in Research Disclosure, Vol. 120, April 1974, p. 12.
008: Research Disclosure Volume 34, 19
June 1975, 13452, U.S. Patent No. 2.642,36
No. 1, No. 3,297,446, No. 3,772,031
No. 3゜857.711, No. 3,901,714, No. 4.266.018, and No. 3,904,41
No. 5, as well as pAg 5-10. as described in British Patent No. 1.315,755. ...5-8 and temperature 30
At ~80°C, sulfur, selenium, tellurium, gold, platinum, -
This can be done using radium, iridium or a combination of these sensitizers. Chemical sensitization is optimally
In the presence of a gold compound and a thiocyanate compound, also US Pat.
Chemical sensitization in the presence of a chemical sensitization aid, carried out in the presence of a sulfur-containing compound or a sulfur-containing compound such as hypo, thiourea compound, or rhodanine compound described in No. You can also. Chemical sensitization aids used include azaindene, azapyridazine,
Compounds known to suppress capri and increase sensitivity during the chemical sensitization process, such as azapyrimidines, are used. Examples of chemical sensitization aid modifiers are described in U.S. Patent No. 2.
No. 131,038, rrI No. 43,411.914, No. 3.554,757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, 138-143.
It is written on the page.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazole furnaces, chlorobenzimidazoles, tetramopenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles. , aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole IN (4?Kl-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptopyrimidines; thioketo compounds such as oxadorinthion; azaindene For example, triazoindenes, tetraazaindenes (% 4-hydroxy substitution (l e 3e 3a e
7) A number of compounds known as anti-capri agents or stabilizers can be added, such as tetraazaindenes), pentaazaindenes, etc. For example, those described in U.S. Pat. No. 3,954,474, U.S. Pat.

The photographic emulsions explicitly used herein may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hop polar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. % useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and conjugated merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline group, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benz Oxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, penzimiguzole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazo-18dine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
5- to 6-membered variants such as rhodanine nucleus and thiobarbic acid nucleus! nuclear can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. A++ Patent No. 2.688,545, Patent No. 2,
No. 977.229, No. 3,397,060, No. 3,5
22゜052, 3,527,641, 3,61
No. 7.293, No. 3,628,964, No. 3,666
．． No. 480, No. 3,672,898, No. 3,679,
No. 428, No. 3゜703.377, No. 3,769,3
No. 01, filJ3.814.609, No. 3,83
No. 7,862, No. 4,026,707, British 11t# No. 1,344,281, Giant Jl, No. 507°803, Japanese Patent Publication No. 43-4936, No. 153-12.375, Japanese Patent Publication No. 153-12.375. No. 52-110.618, No. 52-109,925
listed in the number.

A sensitizing dye is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The timing of adding the dye to the emulsion depends on the emulsion l! which has been known to be useful. It may be a similar stage made by Ill. Although it is usually carried out after the completion of chemical sensitization and before application, chemical sensitization is performed as described in U.S. Pat. Spectral sensitization can be carried out at the same time as chemical sensitization by adding silver halide at the same time, or it can be carried out prior to chemical sensitization as described in % patent publication No. 113,928/1983. Spectral sensitization can also be initiated by addition before the completion of particle precipitation. It is also possible to add these compounds in portions as taught in U.S. Pat. No. 4,225,666, i.e. some of these compounds are added prior to chemical sensitization and the remainder is added prior to chemical sensitization. It is also possible to add it after the sensitization, as described in U.S. Pat. No. 4,183.
．． No. 756, or at any time during silver halide grain formation.

The amount added is 4X1ji6~ per mole of halodane 11!
Although 5 xio moles can be used, about 5 x 10 to 2 x lO moles are more effective for the more preferred silver halide grain size of 0.2 to 1.2 µm.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure ■t@m17643 (December 1978) and 4It@m18716 (November 1979), and the relevant sections are summarized in the table below. Ta.

Additive type RD17643 RD187
161 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3
Spectral sensitizers, pages 23-24, page 648, right hand to super sensitizers, page 649, right column 4
Brightener, page 24 5 Antifogging agent, page 24-25 Page 649 right column and stabilizer 6 Light absorption, page 25-26 Page 649 right column ~ Filter dyeing Page 650 Antifogging agent, ultraviolet absorber 7 Anti-stinting Agent page 25 right @ page 650 left to right column 8 Dye image stability page 25 agent 9 Hardener page 26 page 651 left - lO binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right column 12 Coating aid agent,
Pages 26-27 Page 650 Right column Surfactant 13 Static Page 27 Same as above Inhibitor Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent No. 4,411.987 and (B)
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 4,435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Al 7643, described in the patents listed in ■-CG.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3.501, No. 4,02λ620, No. 4.32
No. 6,024, No. 4,401,752, No. 4.2
48,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425,020, British Patent No. 1.476.760,
U.S. Patent No. 3,973.968, U.S. Patent No. 4,314,0
No. 23, No. 4,511.649, European Patent No. 249
．． No. 473, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, No. 4,351,897, European Patent No. 73.636, US Patent No. 3,061,432, US Patent No. 3.725,067, Research Disclosure No. 424220 (June 1984) ), JP-A-60-33
No. 552, Research Disclosure 424230
(June 1984), JP-A No. 60-43659, No. 6
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, U.S. Patent No. 4
, 500.630, 4.540.654, 4,556,630, International Publication WO88104795
Particularly preferred are those described in No.

Cyan couplers include phenolic and 7-tall couplers, and are disclosed in U.S. Patent No. 4,052.212.
No. 4,146,396, $4.228.2
No. 33, No. 4,296,200, No. 2,369.
No. 929, No. 2.801,171, No. 2,772
．． No. 162, No. 2,895,826, No. 3,77
2.002, 3.758.308, 4.3
No. 34.011, No. 4.327,173, West German Patent Publication No. 3,329,729, European Patent No. 121.36
No. 5A, No. 249,453A, U.S. Patent No. 3.44
6,622, 4,333.999, 4,7
No. 75.616, No. 4,451,559, No. 4,
No. 427.767, No. 4,690.889, No. 4
, 254.212, 4,296,199, and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming Kaglar are U.S. Pat. No. 3,451,820, U.S. Pat.
No. 4,576,910, British Patent No. 2.102°137, European Patent No. 341,188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2.125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3.234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure 17643.
- Section G, U.S. Patent No. 4,163.670, Special Publication No. 1983
-39413, U.S. Patent No. 4004.929, U.S. Patent No. 4.138,258, British Patent No. 1.146,36
The one described in No. 8 is preferred.

In addition, the fluorescent dye released during coupling as described in U.S. Pat. !
Couplers that correct absorption, U.S. Pat.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with the active agent to form a dye as described in No. 20.

Force molecules that release photographically useful residues upon coupling can also be preferably used in the present invention. The DIR capler releasing the development inhibitor is the aforementioned RD 17643.
, Patent described in Section ■-F, JP-A-57-15194
No. 4, No. 57=154234, No. 60-184248
Preferred are those described in US Pat. No. 63-37346, US Pat. No. 63-37350, US Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097°140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other compounds that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat.
1, 4.338,393, 4.310,61
Multi-equivalent coupler described in No. 8 etc., JP-A-60-1859
DIR redox compound compound power output graph-IR coupler emission power output graph-IR coupler emission redox compound or D
IR redox releasing redox compound, European Patent No. 17
3. Couplers R, D, A1144 which release dyes that change color after separation as described in Nos. 302A and 313°308A.
9, l'Fi124241, JP-A-61-201247
Bleach accelerator release power 1r described in No. 1, etc., U.S. Patent No. 4,
555,477, couplers that release leuco dyes as described in JP-A-63-75747, and couplers that release fluorescent dyes as described in U.S. Patent No. 4,774, Class 1. etc.

The powder used in the present invention can be introduced into the light-sensitive material by a conventional dispersion method.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-t-amylphenyl) 7-talate, bis(2,4-t-amylphenyl) isophthalate, bis(1,1-zoethylglobil) 7-thalet), phosphorus Acids are phosphonic acid esters ()
+7 phenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, triptoxyethyl phosphate)%! J chloroglopyruphosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amide@(N
, N-diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpichylidone, etc.), alcohols and phenols (stearyl alcohol, 2,4-di-tart-amylphenol, etc.),
Aliphatic carboxyl esters (bis(2-ethylhexyl) sepacate, dibutyl phthalate, glycerol derichrate, isostearyl lactate, trioctyl citrate, etc.), aniline visiting conductor (N.

N-dibutyl-2-butoxy-5-t@rt-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and di-methylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. It is written in the number etc.

The color photosensitive material of the present invention contains phenethyl alcohol and 1m! j62-272
No. 248 and 1. described in JP-A No. 1-80941.
2-Benzinthiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or for movies, color reversal film for slides or television, color eeper, color positive film, and color reversal eeper.

When the present invention is applied to a color light-sensitive material, at least IJII of the silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer may be provided on the support ( , the number of halogenated emulsion scraps and non-photosensitive layers, and IwI
IK is not particularly limited, but typically has at least one photosensitive layer on the support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. It is a silver halide photosensitive material, and the photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light. In general, an arrangement of unit photosensitive layers is arranged from the support side to 1IK, an it'-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are placed within the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer is disclosed in Japanese Patent Application Laid-Open No. 61-43748, (b) 59.
-113438, l'ff159-113440,
No. 61-20037, No. 61-20038 Akira #! It may contain a coupler DIR compound as described in the book (and may contain a color mixing inhibitor as commonly used).

A plurality of silver halide emulsions RI constituting each unit photosensitive layer
As described in German Patent No. 1,121.470 or British Patent No. 923.045, I can preferably have a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. Usually, it is preferable to arrange the halogen emulsion layers so that the halogen emulsion layers gradually decrease in l&light intensity toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, II!
As described in Japanese Patent Publication No. 57-112751, No. 62-200350, No. 62-206541, No. 62-206543, etc., there is a low-sensitivity emulsion layer on the side far from the support, and a side close to the support. A high-sensitivity emulsion layer may be provided.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer # (EL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer m (GH) / low sensitivity green sensitive layer (GL )/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitivity # (RL), or B H/B L/G L/G ) I/RH/R
In order of L or BH/BL/GW/GL L/RL/RH
They can be installed in the following order:

Furthermore, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/GH/
R) They can also be arranged in the order of I/GL/RL. Furthermore, as described in Japanese Patent Application Laid-open Nos. 56-25738 and 62-63936, blue-sensitive NI/G L/RL/G H/RH are arranged in the order from the farthest side from the support. You can also do that.

In addition, as described in F849-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. One example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is arranged and the photosensitivity decreases sequentially toward the support. Even in a case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464 BA#, medium-sensitivity is The emulsion layer/high sensitivity emulsion layer/low sensitivity emulsion layer is arranged in this order.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion 81/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663.2
No. 71, No. 4.705.744, -1 No. 4,707
．． No. 436, tvf Kaisho 62-160448, same 63
BL and GL described in the specification of No.-89850.

It is preferable that a multilayer effect donor # (CL) having a different spectral sensitivity distribution from the main phosphor layer such as RL is arranged adjacent to or close to the main phosphor layer.

As mentioned above, the layer structure and arrangement of the layers can be selected depending on the purpose of each photosensitive material.

In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not coupled in advance. .

The fine-grain silver halide has a silver bromide content of 0 to 100 moles, and may contain silver chloride and/or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
02 to 02 μm is more preferable.

Fine-grain silver halide is different from ordinary photosensitive silver halide.
It can be prepared by the following method. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, before adding this to the coating solution, triazole-based, azoindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium compound, a mercapto compound, or a zinc compound.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Al7643, and (b)bian 18716
It is described from the left column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25° C. and a relative humidity of 55 degrees (2 days), and the film swelling rate Tl/2 can be measured according to a method known in the art. For example, Knee Green (A, Gr...!I
) et al. Photographic Science &
Engineering (Photogr, Sei, En
By using a swellometer of the type described in Volume 19, Issue 2, pages 124-129,
Can be measured using Tl/2t'i color developer at 30°C for 3 minutes.
The maximum swollen film thickness of 90 inches reached when treated for 5 seconds is defined as the saturated film thickness, and is defined as the time until reaching 1/2 of the saturated film thickness.

The membrane swelling rate Tl/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula: (maximum swollen film thickness -
Film thickness)/Ml: Can be calculated according to the thickness.

The color 4 true light-sensitive material according to the present invention includes the above-mentioned RD, A
17643, pages 28-29, and direction 418716, 6
The development process can be carried out by the usual methods described in the left column to the right column of 51.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phenylene diamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide etheraniline, 3-methyl-4-amino-N-ethyl-β
-methoxyetheraniline and their sulfates, hydrochlorides, p-1 luenesulfonates, and the like.

Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfur has particularly strong properties. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain buffering agents such as alkali metal acid salts, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains a development inhibitor or an anti-capri agent. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive auxiliary developing agents such as g-1-phenyl-3-pyrazolidone, viscosity Imparting agent, aminopolycarzanic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocal? Various chelating agents such as phosphoric acid, for example, ethylenediaminetetraacetic acid,
Nitro compounds, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid,
Typical examples include nitrilo-N,N,N-)+7methylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-/(0-hydroxyphenyl e￥ acid), and Sowara salt. I can do it.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. Ren's black and white developer contains known black and white developing crude drugs such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or 7-minophenols such as N-methyl-p-7 minophenol. can be used alone or in combination.

The - of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but generally it is less than 3 m2 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, −
You can also do the following: When reducing the amount of replenishment, it is preferable to reduce the contact area of the processing tank with the sudden air to prevent evaporation of the liquid and air oxidation.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to installing a shield such as a floating lid on the photographic processing solution in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The processing time for the color developing agent is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and a high concentration of the color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process, or it may be carried out separately in a bleach-fixing process (8+). Furthermore, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Treatment with two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be carried out as desired depending on the purpose. Examples of i94 bleaching agents include compounds of polyvalent metals such as iron(II), peracids, quinones, nitro compounds, etc. Typical bleaching agents include organic complex salts of iron(1), such as ethylenediamine tetra Aminopolycarboxylic acids such as acetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, meteliminodiacetic acid, l,3-diaminotetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. etc. can be used. Among these, aminopolycarboxylic acid iron (II) # salts, including ethylenediaminetetraacetic acid iron (m) complex salt and 1,3-diamino 14onetetraacetic acid iron (II) complex salt, are used for rapid processing and environmental pollution prevention. Aminopolycarbonate (It) is preferable from the observation of
Complex salts are particularly useful in both bleaching solutions and super-whitening fixing solutions. The Sa of the bleach solution or bleach-fix solution using these 7-minophoricarboxylic acid iron (11) complex salts is usually 4.0 to 8.
However, to speed up the processing, it is also possible to process with an even lower voice.

Bleach accelerators can optionally be used in the bleach, bleach-fix solutions and their prebaths - specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3.893.858, West Dokko No. 1,290,81
No. 2, Mukai No. 2,059,988, JP-A-53-3273
No. 6, No. 53-57831, 1b-153-3741
No. 8, No. 53-72623, No. 53-95630,
No. 53-95631, No. +53-104232, No. 53-124424, No. 53-141623, li
>353-28426, Research Disclosure No. 417129 (July 1978), etc. Compounds having a mercapto group or disulfide group; Thiazolidine derivatives described in JP-A-50-140129: %
Thiourea derivatives described in JP-A-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Patent No. 3.706°561: West German Patent No. 1.127,71
Iodide salts described in No. 5, JP 158-16,235; West German Patent No. 966.410, PI 3.748.4
Polyoxyethylene compounds described in No. 30;
5-8836? Reamin compounds; Others JP-A No. 49-40.943, JP-A No. 49-59,644, JP-A No. 5
No. 3-94,927, No. 54-35,727, No. 55
Compounds described in No. 26,506 and No. 58-163,940: bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat.
No. 58, West German Patent No. 1,290,812, JP-A-53
-95,630 is preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred, and these bleach accelerators may be added to the photosensitive materials. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Bleach and bleach-fix solutions contain K in addition to the above compounds.

It is preferable to contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have acid dissociation constants (pK
Compounds in which a) is 2 to 5, specifically preferred are diacetic acid and propionic acid.

The fixing agent used in fixing solutions and bleach-fixing solutions can include thiosulfates, thiocyanates, thioether compounds, thioureas, large amounts of iodide salts, etc., but thiosulfates are commonly used. Ammonium thioate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixing solution and the bleach-fixing solution, it is preferable to use a dibasic acid base, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in European Patent No. 294769A. Furthermore, it is preferable to add various aminopolycarmenic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution. The total time for the desilvering process is
It is preferable that the length be as short as possible so long as desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes.

Furthermore, the treatment temperature is 25°C to 50°C, preferably 35°C to
The temperature is 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable to strengthen the stirring as much as possible.A specific method for strengthening the stirring is to impinge a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460. Method and JP-A-62-183
No. 461 uses a rotating means to increase the stirring effect, and furthermore, moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface results in more agitation. There are methods to improve the effect and methods to increase the circulation of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved agitation speeds up the supply of bleach and fixing agent to the emulsion medium, and as a result increases the desilvering speed. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means described in Japanese Patent Laid-Open No. 191259-1912. It is highly effective in preventing deterioration of processing liquid performance. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to desilvering treatment, water washing and/or stabilization steps.

The washing water t in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), countercurrent flow, replenishment method of fist flow, and various other factors. It can be set over a wide range depending on the conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnalof th@5oci@ty of Mot
ion Pietor* andT@1sv1sion
Et+gin@ers Vol. 64, p. 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of washing water t can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the generated suspended matter adheres to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Chlorine-based disinfectants such as inthazolone compounds, thiapendazole, chlorinated sodium incyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Eishu Edited by Japan Society of Technology [Microbial Sterilization, Disinfection, and Anti-Mold Technology J (1982) Japan Society of Industrial Engineers, Japan Society of Antibacterial and Anti-Mold Agents "Encyclopedia of Antibacterial and Antifungal Agents J (1986)
2010) Bactericides listed in K can also be used.

- of the washing water in the processing of the photosensitive material of the present invention is 4 to 9
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 10 minutes.
A range of 30 seconds to 5 minutes at ~40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, all the known methods described in %KOKAI No. 57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photosensitive materials for photography. can be used. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

Over 70- due to water washing and/or replenishment of stabilizing solution
The liquid can also be reused in other processes such as a desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration in addition to water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various gray cursors of color developing crude drugs. For example, U.S. Patent No. 3.342.5
Indoaniline compounds described in No. 97, No. 3,342
．． No. 599, Research Disk μm Jar 14,85
Ship base type compounds described in No. 0 and No. 15,159,
Aldol compounds described in U.S. Pat. No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may incorporate pyrazolidones are described in %W4 No. 56-64339, No. 57-144547, and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Furthermore, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4
, No. 500.626, Monokai No. 60-133449, l
It can also be applied to photothermographic materials described in ql 59-218443, ql 61-238056, European Patent No. 210,660A2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Average iodine content is 24 molt, average equivalent sphere diameter is 0°9 μm
The double twinned particles of were used as seed crystals, and a halogenated *solvent (!I) and sulfuric acid were added in a ceratin water bath solution to adjust the pH to 4.2, and the core-shell ratio was adjusted to 1:2 by the controlled double jet method. An emulsion consisting of twinned grains having an average equivalent sphere diameter of 1.4 μm was formed so that the iodine content of the shell was 4 mol %.

After grain formation, the emulsion was cooled to 35°C, a precipitant was added, and the emulsion was precipitated with sulfuric acid at p) 14.3, washed with desalted water by the flocculation method, and then redispersed at 40°C.

The emulsion thus prepared is called Em-1.

On the other hand, Em-2 is an emulsion prepared by the same process as Em-1 except that the voice before the start of shell formation is changed to 6.5 in the preparation method of Em-1.

For Ern-1 and Em-2, thiosulfonic acid compound 2.1-6 shown in Table A was added 1 minute before the start of shell formation.
．． As shown in Table 1-1, optimum amounts of each of 1-16 were added to the reaction tube to form particles, and the particles were washed with demineralized water and redispersed in the same manner as Em-1 to obtain Em-3 to Em-3. -8
It was created.

Table 1-1 Emulsions Em-1 to Em-8 thus prepared were each optimally sulfur-sensitized using sodium thiosulfate and chloroauric acid.

Emulsions Km-1 to 1 were coated on a triacetyl cellulose film support with an undercoat layer as shown in Table 2.
Samples 1 to 8 were prepared by applying Km-8 and a protective layer, respectively.

Table 1-2 (11 emulsion layers/emulsions...the above emulsions Em-1 to Em-8 (silver 1.7X
IOMojVwt") -Coupler (1,5X 10-'mol/m")t - Tricresyl phosphate (1,10g/m") - Gelatin (2,3097m") (2) Ho 111
JII-2,4-dichlorotriazine-6-hydropxy-1-
Triazine sodium salt (0.08 g/m') and gelatin (1,809/m'') These samples were exposed to light for sensitometry and subjected to color development.

Exposure was carried out in a conventional wedge kiln at 10 seconds and 1/100 seconds.

The light source used was one whose color temperature was adjusted to 4800''K using a filter, and a blue filter (BPN42 manufactured by Fuji Photo Film Co., Ltd.) was used to extract blue light.

The development treatment used here was carried out under the following conditions.

1. Color presentation...2 minutes 45 seconds 38℃2, Bleaching...6 minutes 30 seconds 38℃3, Washing...3 minutes 15
Seconds 24℃4, fixation...6 minutes 30 seconds 38℃5,
Washing with water...3 minutes 15 seconds 24℃6, stable...
3 minutes 15 seconds 38°C The composition of the treatment liquid used in each step is as follows.

Color developer nitrile sodium triacetate 1.49 p
Sodium hydrate 4.0g Sodium carbonate 30.011 Potassium bromide hydroxylamine sulfate 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate Add bleach solution Ethylenediaminetetraacetic acid 2nd Sodium iron trihydrate Ammonium bromide Aqueous ammonia (28%) Ethylenecyamine-Sodium acetate salt Add glacial acetic acid water to fix fixing solution Sodium tetrapolyphosphate Sodium sulfite Ammonium thiosulfate (70%) Sodium bisulfite 1.41 2. 4g 4.5g t 00g 160.0g 25.0IIIj 10.0g 14 117 t'z,og 4.0g 175.0w 4.6g Add water and add 1 to the stabilizing solution: / 8.01Ll water In addition, the concentration of a sample containing 1 was measured using a green filter.

Table 1 shows the photographic performance results of the sample immediately after preparation and after being exposed to an environment of 25°C and relative humidity [60°C for 12 months.
-3. Sensitivity is 0.2 more optical density than Capri
Comparison was made in terms of. The sensitivity display is 1/1 immediately after preparing sample 1.
It is expressed as a relative sensitivity with the sensitivity at 100 second exposure as 100 (both 1/100 second and 10 second are set as 100. The fog value is the value for an unexposed area, and 1/100
The value was the same between seconds and 10 seconds. ).

From Table 1-3, if - is increased to 6.5 without adding a thiosulfonic acid compound during shell formation, the sensitivity immediately after sample preparation is relatively high, but it is accompanied by strong fogging and increases in fogging over time. Sensitivity decreases significantly, which is not preferable. In addition, the sample in which a thiosulfonic acid compound was added during shell formation and had a rating of 4.2 showed little deterioration in photographic properties over time, but the sensitivity itself was low. It can be seen that not only is the sensitivity suppressed and the sensitivity is high, but also the increase in fog and the decrease in sensitivity after aging are small, indicating excellent storage stability.

Example 2 A gelatin aqueous solution (water 1
50 (1/, gelatin 309. KBr79), and while keeping the solution temperature at 40°C, I M AgN0° aqueous solution 58.81 L/and KBr, 96 mot/L%
K.I.O.

After adding 58.8 d of an aqueous solution containing 0.04 rnot/L at a constant flow rate over 1 minute, the temperature was raised to 60°C.

Then 1.76 M ArNO3 aqueous solution and KBr2.
A halogen aqueous solution containing 66 mob/L% KIO, 11 rnoL/L was added for 40 minutes while maintaining pBr 1.9 until the amount of AgNO3 aqueous solution added reached 3001, and then left for 5 minutes.

Furthermore, pBrl was 1.76M in 15 minutes while maintaining 9.
A1NO3 aqueous solution and KBr2.66 moA/L
%KIO.

AgNO5, a halogen aqueous solution containing 11 mot/t
After adding 2331 of the aqueous solution until it was consumed, a halogen aqueous solution of the same concentration of AgN0.
gN0° aqueous solution was added until 1001117 gN0° aqueous solution was consumed and the emulsion was cooled to 40°C. Desalination water washing and dispersion are Em
It was carried out in the same manner as the preparation method of -1. The emulsion thus made is called Em-9.

Em-10 is an emulsion prepared in the same manner as Em-9 except that an aqueous AgNO3 solution was added for 5 minutes to adjust pBr to 3.8.

AgNO3 for 5 min for Em-9 and Km-10
10 seconds before the start of addition of the aqueous solution, add each of the thiosulfonic acid compounds 1-2.1-5.1-6゜1-21 in the optimum amounts as shown in Table 2-1, as in En+-1. Em-1 to Em-18 were prepared by desalting, washing with water, and redispersing using a conventional method.

Table 2 - Emulsions Em-9 to Em-18 prepared in this way are
Sodium thiosulfate 6.0X10 mol/A [mol,
Optimal gold/sulfur sensitization was carried out using chloroauric acid (8.5 x 10-' mol/Ag mol) and thiocyanate (thiocyanate) 2.0 x 10-' mol/Ag mol.

Em-9 to E were prepared in the same manner as the coated samples shown in Example IK.
Samples 9 to 18 were prepared by applying m-18. However, the coating amount of the emulsion layer is Ag: 2, lX10 mol/m" for the emulsion, and 1.5 X l O-' mol/W for the coupler.
1! It is.

These samples were subjected to sensitometric exposure in the same manner as in Example 1, and color development processing was performed.

The results of photographic performance immediately after preparing the sample and after 12 months at a temperature of 250°C and a relative humidity of 60°C, and after exposure for 17,100 seconds immediately after preparing the sample at a temperature of 30°C and a relative humidity of 60°C. Table 2-2 shows the photographic performance results of the nine samples left for several months.

The definition of sensitivity is the same as in Example 1, and is expressed as relative sensitivity, with the sensitivity at I/100 second exposure immediately after sample 9 being prepared as 100.

From Table 2-2, it can be seen that the samples of the present invention have low fog and high sensitivity, and have excellent stability over time with little fog and sensitivity fluctuations over time from the time the sample is prepared until it is exposed. In addition, it was found that the sample was not sensitized even under forced conditions by applying moist heat after exposure (it was also found to be excellent in terms of latent image storage stability).

Example 3 v11m1 in Example 1! After particle formation for Em-1, thiosulfonic acid compound 1 was added as an oxidizing agent for silver.
-2.1-16 or hydrogen peroxide solution (H2O2) as shown in Table 3-1, respectively, is added in an appropriate amount and then precipitated with sulfuric acid at pH 4.3. in! ! Em-19 to Em-
21.

Next, after forming particles using the same method as Em-1 and -1, add an appropriate amount of ammonium sulfate and precipitate at 6.8 K, but use the same method as Em-1! ill#! (L9 emulsion)
, n-22.

In addition, in Em-22, as an oxidizing agent for the steel after particle formation, the optimum amount of thiosulfonic acid compound l-2゜1-16 or B2O2 was added as shown in Table 3-11c, and then an appropriate amount of ammonium sulfate was added. Emulsions prepared in the same manner as Em-22 and -1, except for sedimentation at step .8, are designated Em-23 to Em-25, respectively.

Em-26 is an emulsion prepared in the same manner as Em-1 prepared in Example 1 except that Fi'i during shell formation was changed to 8.0.

In Em-26, as an oxidizing agent for grain-forming vk silver, thiosulfonic acid compound 1-2.1-16 or H2O2 was added in the optimum amount as shown in Table 3-1, and then precipitated with sulfuric acid at -43. Em -26 except for
Emulsions prepared in the same manner as Em-27 to Em-29
shall be.

In Em-26, after particle formation, an appropriate amount of ammonium sulfate was added and sedimentation was performed at -8,1.
An emulsion prepared in the same manner as in Example 6 was designated as Em-30.

In Era-27, after grain formation, thiosulfonic acid compound 1-2.1-16 or H2O2'Jk was added as an oxidizing agent for silver in the optimum amount as shown in Table 3-IK, and other than precipitation in p) 18.1. are emulsions prepared in the same manner as Em-27 and Em-31 to Em-31, respectively.
33.

Emulsions Em-1 and Em-19 to Em produced in this way
Emulsions of each emulsion of -33 were optimally sensitized with gold and sulfur using sodium thiosulfate and gold acid.

Eml and E were prepared in the same manner as the coated samples shown in Example 1.
Sample 1 and Sample 1 were coated with m-19 to Em-33.
Samples 9 to 33 were prepared.

These samples were subjected to sensitometric exposure in the same manner as in Example 1, and color development processing was performed.

The results of photographic performance immediately after the sample was prepared and after 12 months at a temperature of 25 degrees Celsius and a relative humidity of 60 degrees. The results of photographic performance when left for several months are shown in Table 3-2.

The definition of sensitivity is the same as in Example 1, and is expressed as relative sensitivity, where the sensitivity at 1/100 second exposure immediately after the preparation of sample 1 is taken as lOO.

From the results in Table 3-2, it can be seen that the samples coated with the emulsion of the present invention in which P1'1 during sedimentation was 6.8 or 81 and an oxidizing agent for silver was added had high sensitivity with almost no increase in fog. I understand that. Furthermore, it can be seen that the photosensitive material exhibits excellent performance in terms of storage stability over time after production and before use, and storage stability after exposure and processing.

Further, it can be seen that the effect of the present invention is more effective when both the value during shell formation and the time during sedimentation are increased.

Example 4 In Example 1, l! 1m! In the same manner as for Em-1, except that - during redispersion is set to 4.8, 6.2, and 11.5, respectively! ! The emulsions prepared by Ill are designated as Em-34+Em-35+Em-36, respectively.

For each of Em-34, Em-35, and Em-36, thiosulfonic acid compound 1-2.1-1 (1, as shown in Table 4-IK 5 Em-37 to Em-42 were prepared by adding the optimum amount to each.

Em-34 to Em-42 -6, 2, PAN8 respectively
．． 6, and then optimally gold/sulfur sensitized with sodium thiosulfate and chloroauric acid to prepare an emulsion.

Em-34~
Samples 34 to 42 were prepared by applying Eyn-42.

These samples were subjected to sensitometric exposure in the same manner as in Example 1, and color development processing was performed.

Table 4-2 shows the results of photographic performance immediately after the sample was prepared and after it had been left in an environment of 25 degrees Celsius and relative humidity 60 degrees for 12 months.
Shown below.

From Table 4-2, the sample prepared by dispersing the emulsion of the present invention with -6.2 at the time of redispersion and adding a thiosulfonic acid compound exhibits high sensitivity with almost no increase in fog, and has a poor shelf life. It can be seen that it is superior in terms of

In addition, in a comparative example where the pH was raised too high to 11.5,
It can be seen that although the sensitivity immediately after sample preparation is relatively high, addition of a thiosulfonic acid compound causes strong fog, and is also unfavorable in terms of storage stability, as it increases fog and decreases sensitivity.

Example 5 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) The coating amount is fi for silver halide and colloidal silver.
The amount of silver expressed in m'/m', and the amount of silver per mole of silver halide in the same layer for sensitizing dyes, and the amount of silver per mole of silver halide in the same layer for sensitizing dyes. Expressed in moles.

1st layer: Anti-halation dark black colloidal silver Silver coating amount 0.2 Gelatin 2.2t7V-10・l UV-20,2 Cpd-10,04 Cpd-20,02 Solmer 1 0.30So
lmer 2 0.01 2nd NI
: Intermediate layer fine grain silver iodobromide (Afll, 0 molti (equivalent sphere diameter 0.07 μm) silver coating amount 0.1
5 gelatin 1.0E x
C-40.03 Cpd-30.2 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (Ag150 molti, surface height AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21 mm) , tabular grain, diameter/thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 molti, internal cylinder AgI type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18 H, dodecahedral particles) Silver coating amount 0.40 Gelatin 1.0EX
S-14,5X10-'molExS-21,5X10-4-fnylExS-3
0,4X10-'mol Ex C-10,50 ExC-20,11 ExC-30,009 Ex C-40,023 Solv-10,24 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag48.5 mortise, internal cylinder AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25 tres, plate-shaped particles, diameter/thickness ratio 3°0) Trowel application II 0.85 gelatin 0.7ExS- 13×1
0-'mol ExS-21 Silver bromide emulsion ■ Trowel application 11 1.50 Gelatin 0.6ExC-20
,08 Ex C-40,01 Ex C-50,06 Solv-10,12 Solv-20,12 6th layer: Intermediate layer gelatin 1. OCp d
-40,1 S o l v -10,1 1st υ[1st green-sensitive emulsion layer silver iodobromide emulsion (Ag15.0 molten, surface height AgI type, equivalent sphere diameter 0.9 μm% variation in bead equivalent diameter) Coefficient 21, tabular grains, diameter/thickness ratio 7.0) Silver coating amount 0.28 silver iodobromide emulsion (*gI 4.0 mol, internal cylinder AgI type, equivalent sphere diameter 0.4 μm, equivalent sphere diameter Coefficient of variation of 18 h, dodecahedral particles) Silver coating amount 0.16 gelatin
1.2ExS-55X10
Mol ExS-62X10 Mol ExS-71 Silver emulsion (AgI 8.5 molt, internal high iodine type, equivalent sphere diameter 1.0 μm, coefficient of variation of 1 sphere equivalent diameter 25 mm, plate-like grains, diameter/thickness ratio 3°0) Silver coating amount 0.57 Gelatin 0. 35ExS-53,
5xlo-'mol ExS-61,4X10-'mol ExS-70,7XIF'mol ExM-10,12 ExM-20,01 EXM-30,03 Sol Mer 1 Sol Mer 4 9th @: Intermediate layer gelatin Sol Mer 1 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion ■ Silver coating amount Gelatin xM-4 XC-4 Ex M-6 pd-5 Solmer 1 11th layer: Yellow filter layer pd-6 Gelatin Solmer 112 layers: middle layer gelatin pd-3 0,15 0,03 0,5 0,02 1,3 0,8 0,04 0,005 0,01 0,01 0,2 0,05 0,5 0 , 1 0, 5 0, 1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mole, uniform iodine type, equivalent sphere diameter 0.55 - μm 1 Rin equivalent diameter coefficient of variation 25 mm, tabular) Grain diameter/thickness ratio 7゜0) Silver coating amount Gelatin xS-8 xY-1 xY-2 olv-1 14th layer: @2 blue-sensitive emulsion layer Silver iodobromide emulsion (Asr1190 molten, internal high AgI type, sphere Coefficient of variation of sphere equivalent diameter to equivalent diameter 1.0μ, octahedral particles) Silver coating amount Gelatin xS-8 19 0.3 2X10-'mol 0.22 0.07 15th skin: Intermediate layer fine grain silver chloride hydrogen chloride water AgI 2 molti, homogeneous iodine type,
Equivalent ball diameter 0.13j! m) Silver coating amount Gelatin 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion ■ Silver coating amount Gelatin xY-1 Solmer 1 177il: First protective layer Gelatin UV-1 UV-2 Solmer 1 Sol Mar2 18th layer: 2nd theory layer fine grain silver chloride (equivalent sphere diameter 0.07 μm) fl! Coating amount 0.2 0.36 1.55 0.5 2 0.07 1.8 0.1 0.2 0.01 0, Ol 0.36 Gelatin 0.7 Polymethyl methacrylate particles 0.2 (Diameter: 1.5 μm) W-10.02 H-10.4 Cpd-71.0 In addition to the above, each layer contains B-1 (total o, zo9/m, 1
．． 2-benzisothiazolin-3-one (approximately 200% relative to gelatin), n-butyl p-hydroxypenzoate (approximately 1,000111m), and 2-phenoxyethanol (approximately 10,000% relative to gelatin) were added. .

UV-1: X/7=7/3 (weight ratio) UV-2: ExC-1 ExC-2 0) 1 H2 Summer ExC-5 OCR2CH2SCHCOOH Betsu 12H25 ExM-6 ExY-1 t ExM-2 pd-1 pd -2 pd-a H pd-4 pa-5 pd-5 H pd-7 -1 C8F, , 80□NHα2■21□α12α2N (acceptable).

-1 0M2= CH3O2CM2C0NIII-CH2豐CH,= CFISO2CH2■廟-α2-1 EXS-1 ExS-3 (LH2)3SL) h~LL:2t15ノ3rS-5 ExS-6 ExS-7 Solmer 1 olv- 2 SO1mer 4 For the chemically sensitized emulsion Em-1=Em-8 created in Example 1, red-sensitive, green-sensitive, and blue-sensitive emulsions were created using the following dye groups, respectively. did.

・Dye group l (red-sensitizing dye) Sensitizing dye ExS-12,0XIO mol/Ag mol ExS
-20,6X10-' z t EXS-30,2XIO-' -Dye group 2 (green-sensitizing dye) Sensitizing dye ExS-52,0X10 mol/Ag mol E
xS-60,8XlO-' t l ExS-70,8X10-4 ・Dye group 3 (blue-sensitizing dye) Sensitizing dye ExS-91,5X10-' mol/A g mol No. 5 of the above-mentioned multilayer color photosensitive material , 10th layer, 16th layer
Silver iodobromide emulsion #1. Multilayer color light-sensitive material samples 501 to 508 were prepared by replacing Il and IIl with K as shown in Table 5-IK for the emulsions spectrally sensitized to the respective color sensitivities described above.

Table 5-1 These samples were exposed to light for sensitometry and subjected to the following color development process.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table 5-2.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 501 was taken as 100.

Processing method Color development processing was carried out according to the following processing steps.

Color development fi 3 minutes 15 seconds 38℃ Bleached white 6 minutes 30 seconds 38℃ Wash with water 2 minutes 10 seconds 24℃ Fixed arrival 4 minutes 20 seconds 38℃ Water washing 3 minutes 15 seconds 24℃ Stable 1 minute 05 seconds 38℃ The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriamine pentaacetic acid 1-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2-methyl Add aniline sulfate solution and bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate 1.0Ii 2, Og 4.0g 30.1 1.4g 1.3aI9 2, 4 lI 4 .5Ii 1.0t 10.0 100.0g 10.0g xsO,0g 10.0g Add water - Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate water bath solution (70 g) Iffi Add sodium sulfate water 11 Stabilizing liquid formalin (4o%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add water 1, OL 6.0 1.0g 4.0g 175, Qm 4.6g 1, O4 6 2,0IIL1 0.3g 1, Ot As is clear from the results 5-2, the photosensitive material of the present invention has the effect of increasing sensitivity with almost no increase in capri.

Further, when the photographic performance after redness was examined in the same manner as in Example 1, it was found that the photographic material of the present invention exhibited good storage stability.

Example 6 Samples 501 to 508 of the present invention and comparative examples were exposed to Example 5 and rcl, +-like KjI, and then processed in the manner described below using an automatic gI machine.

Processing method Step Processing time Processing temperature Color development g1
3 minutes 15 seconds 38℃ bleaching 1 minute 00
Seconds 38℃ bleach fixing 3 minutes 15 seconds 38
℃ water washing (1140 seconds 35℃ water washing (ri 1 minute 00 seconds 35℃ stable)
Drying at 38°C for 40 seconds 55°C for 1 minute and 15 seconds Next, the composition of the treatment solution will be described.

(Color developer) Diethylenetriaminepentaacetic acid l-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N-(β-human is xyethyl) Add amino2-2-methylaniline sulfur brine (bleach solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt (Unit I) 1.0 3.0 4.0 30.0 1.4 1.5 - 2.4 4.5 1.0L 10.05 (Unit y) 120.0 10.0 Ammonium bromide Ammonium nitrate Bleach accelerator 100.0 10.0 o, oos mol Ammonia water (27 T) Water Add 11 (Bleach-fix solution) Ethylenediaminetetraacetic acid diiron ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium thiosulfite ammonium aqueous solution (70%) Aqueous ammonia (27ts) Add water and add H (Washing solution) 15.0117 1, OL 6.3 (unit g) 50.0 5.0 12.0 240.0 m/ 6, Ov 1, OL 7.2 Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite manufactured by M&Haas). Water was passed through a mixed bed column packed with IR-120B) and OH type anion exchange resin (Amberlite IR-400) to reduce calcium and magnesium ion concentrations to below ■/, followed by dichlorination. 20 μ/L of sodium incyanurate and 1.5 p/L of sodium sulfate were added. - of this solution was 6.5-7.
It is in the range of 5.

(Stabilizing liquid) (Unit g) Formalin (37 g) 2.0% Polyoxyethylene-P-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1 .0tp)1
5.0-8.0 Sample 5 of the present invention
Samples No. 06 to No. 508 obtained good results by this treatment as well as in Example 5.

Example 7 Sample 5 of the present invention and comparative example After exposing to the flow side 5 and lit, It was processed using the method described below.

Processing method Process Processing time Color development g#2 minutes 30 seconds Bleach fixing 3 minutes 00 seconds Wash with water (1120 seconds Wash with water (2120 seconds Stability 20 seconds Dry 50 seconds Next, the composition of the treatment p solution will be described.

1 color developer] diethylenetriaminepentaacetic acid 1-hydroxyethylidene- 1,1-diphosphonic acid sodium sulfite potassium carbonate potassium bromide Execute 01-508 using automatic development Processing temperature 40℃ 40℃ 35℃ 35℃ 35℃ 65℃ (Unit: L) 2.0 potassium iodide and druxylamine sulfate 4-[N-ethyl-N-( β-Hydro Mino]-2-methylanili sulfur salt add water (II white fixer) Ethylenediaminetetraacetic acid diiron ammonium dihydrate Ethylenediaminetetraacetic acid di sodium salt sodium sulfite Ammonium thiosulfate water soluble liquid (70%) Acetic acid (989&) bleach accelerator 1.5■ 2.4 4.5 1.Ot. 10.05 (Unit: g) 50.0 5.0 12.0 260.0jlJ 5.01 0, O1 mol S.H. Add water X, 0t-6.

(Washing liquid) Tap water was filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite rR-400 manufactured by Rohm and Haas) to form a nine mixed bed column. Water was passed through the reactor to reduce the concentration of calcium and magnesium ions to 3/l, and then 20119/l of sodium isocyanurate dichloride and 1.5 y/l of sodium sulfate were added.

The - of this liquid is in the range of 6.5-7.5.

(Stabilizing liquid) (Unit i)
Formalin (37cm) 2. O1u polyoxyethylene-p-mo/nonylphenyl ether (average degree of polymerization 10) 0.3 ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.01 pHs, o
-s,.

Samples 102 to 104 of the present invention had good results as in Example 2 also by this treatment.

Example 8 On a subbed cellulose nine triacetate film support,
Each layer having the composition shown below was coated in a multilayer manner to produce a multilayer color photosensitive material.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in I/m' units, and for halogenated complexes, they indicate the coating amount in terms of silver. However, for sensitizing dyes, the coating amount in the same layer The coating amount per mole of silver tetragnide is shown in mole units.

1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (middle N
) 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,07 EX-30,02 EX-120,002 U~I O,06U-20
,08 0-30,10 HBS-10,10 HBS-20,02 Gelatin 1.04 Third layer (donor N for weight effect on red-sensitive layer) Emulsion J
Silver 1.2 Emulsion K Silver
2.0 Sensitizing dye Y 4X10-'E
X-100,10 EX-140,10 HBS-10,10 HB8-2 0.10
4th layer (intermediate layer) X-5 His -1 Gelatin 5th layer (first red-sensitive emulsion layer) Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye m X-2 X-lo -1 - 2-3 B8-1 Gelatin 6th layer (second red-sensitive emulsion NJ) Emulsion G Sensitizing dye! O,040 0,020 0,80 Complex 0.25 Silver 0.25 1.5 X l O'-' 1.8 X 10-5 2.5 X l O"' 0.335 0.020 0.07 0.05 0.07 0.060 0.87 Silver 1.0 LOXIO"" Sensitizing dye ■ Sensitizing dye ■ X-2 X-3 X-10 -1 -2 -3 1g gelatin 7 layers (third red sensitivity Emulsion layer) Emulsion D X-3 X-4 X-2 B5-1 ES-2 Gelatin 8th layer (intermediate layer) ,os.

O,015 0,07 0,05 0,07 1,30 silver 1.60 0.010 o,os.

O,097 0,22 0,10 1,63 0,040 0,020 Gelatin 9th layer (green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-1 X-7 X-8 ) IBS -1 ) [B5-3 Gelatin! 10 layers (second green-sensitive emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ 0.80 Silver 0.15 Silver 0.15 3DXIO-'1.0X10-'3J3X1O-' 5.0X10- 5 0.260 0.021 0.030 0.005 0, l 00 0.010 0.63 Silver 0.45 2, I X I 0-5 7.0X10-5 2.6X10''''4 Sensitizing dye N 5.0X10-'
EX”-60,094 EX-220,01S EX-70,026 HBS-10,160 HBS-30,008 Gelatin 0.5° 11th m
(Third green-sensitive emulsion Ml) Emulsion E Silver 1.2EX-13
0,015 EX-110,100 EX-10,025 HBS-10,25 EBB-20,10 Gelatin 1.54 12th layer (yellow filter layer) Yellow colloidal silver Silver 0. oSEX-
50,08 HBS-10,03 Gelatin 0.95 13th layer CMx blue sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ X-9 X-8 ) IBS-1 Gelatin 14th layer (#!21 sensitive Emulsion! II) Emulsion G Sensitizing dye ■ X-9 X-10 B5-1 Gelatin 15th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ X-9 Chain 0.08 Silver 0.07 0. 07 3.5 X 10" 0.721 0.042 0.28 1.10 Silver 0.45 2, I 4 0.20 HBS-10,07 Gelatin 0.69 16th layer (
1st layer) Emulsion I Silver 0.20U-40.1
1 U-50,17 HBS-10,05 Gelatin 1. OO 17th layer (
2nd protective i# layer) Polymethyl acrylate particles (Il, diameter approximately 1.5 μm) 0.54S
-10,20 Gelatin 1,20 In addition to the above ingredients, each layer contains gelatin hardening agent H-1%EX-14~
21 and a surfactant were added.

X-1 X-3 H (1)C4H,0CONH Oc)12CH2SOI2CO2H Dylphosphate-n-butyl phthalate sensitizing dye l Sensitizing dye■ Sensitizing dye■ Sensitizing dye V Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ -1 CH2-CH-3o2-CH2-CONH-CH2CH
2-CH-SO2-CH2-CONH-C12x-14 OONm X-15 x-16 Polyvinylpyrrolidont? Copolymer of ribinyl alcohol X-17 x-18 H x-19 ,2-Benzinthiazolin-3-one Ex-20 n-butyl p-hydroxybenzoate Chemically sensitized emulsions Em-9 to Em-18
In contrast, red-sensitive, green-sensitive and blue-sensitive emulsions were prepared using the following dye groups.

- Dye Glue - Glue A (red-sensitive dye) - Dye Glue 7B (green-sensitive dye) Spectral sensitization of the emulsions E and E of the 7th layer and 11th layer of the multilayer color light-sensitive material described above to each color sensitivity. The resulting emulsions were replaced as shown in Table 8-1, and multilayer color photosensitive material samples 801~
Create 810.9.

Table 8 - These samples were subjected to sensitometric neutralization, color development processing similar to Example 5 and fi5j, and #degree measurements.

It was confirmed that the color photosensitive phase family of the present invention exhibits excellent photomagnetic performance also in the emulsion and multilayer color photosensitive material used in this example.

However, when the same preservability test as in Example 5 was conducted, it was confirmed that the color light-sensitive material of the present invention exhibited good performance even in terms of preservability.

Showing items 1995 Patent Application No. 7/? Z issue Ming name Silver halide photographic material 3. Person who makes corrections Relationship to the case: Patent applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 1. 2. Departure 5. Target of correction: Specification 6. Contents of amendment Engraving of the statement (no changes to the contents) I will submit.

Claims (10)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in the silver halide emulsion layer has a pH of 5.
0 to 11.0, and is produced through a process other than chemical sensitization and a process in which at least one oxidizing agent for silver is present. (2) The silver halide photographic material according to claim (1), wherein the oxidizing agent for silver is at least one compound represented by the general formula [I], [II] or [III]. [I] R-SO_2S-M [II] R-SO_2S-R^1 [III] R-SO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different. Often represents an aliphatic, aromatic, or heterocyclic group, M represents a cation, L represents a divalent linking group, and m is 0 or 1. The compounds represented by formulas [I] to [III] may be polymers containing divalent groups derived from the structures represented by [I] to [III] as repeating units. (3) In the manufacturing process of silver halide emulsion, the pH is 5.
．． 2. The silver halide photographic material according to claim 1, wherein the step in which the particle size is 0 to 11.0 is a grain forming step. (4) The pH of the grain forming step of the silver halide emulsion is 6.
3. The silver halide photographic material according to claim 3, which has a molecular weight of 2 to 11.0. (5) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in the silver halide emulsion layer has a pBr of 2.0 to 5 at the time of grain formation. 1. A silver halide photographic light-sensitive material, characterized in that it is produced through a step in which the oxidizing agent for silver is .0, and a step in which at least one oxidizing agent for silver is present. (6) The silver halide photographic material according to claim (5), wherein the oxidizing agent for silver is at least one compound represented by the general formula [I], [II], or [III]. [I] R-SO_2S-M [II] R-SO_2S-R^1 [III] R-SO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different. Often represents an aliphatic, aromatic, or heterocyclic group, M represents a cation, L represents a divalent linking group, and m is 0 or 1. The compounds represented by formulas [I] to [III] may be polymers containing divalent groups derived from the structures represented by [I] to [III] as repeating units. (7) In the manufacturing process of silver halide emulsion, the pH is 5.
．． The silver halide photographic light-sensitive material according to claim 1, wherein the step of 0 to 11.0 is a desalination water washing step. (8) The pH of the silver halide emulsion desalination washing step is 6.
7. The silver halide photographic material according to claim 7, which has a molecular weight of 2 to 11.0. (9) In the manufacturing process of silver halide emulsion, the pH is 5.
．． 2. The silver halide photographic light-sensitive material according to claim 1, wherein the step in which the particle size is 0 to 11.0 is a redispersion step. (10) The pH of the silver halide emulsion redispersion step is 6.
The silver halide photographic material according to claim 9, wherein the silver halide photographic material has a molecular weight of 2 to 11.0.